Ferrocene-containing polyphosphate and phosphonate esters were synthesized by the solution polycondensation method. The structure of the polymers was confirmed using various spectroscopic techniques. The formation of two types of chain blocks was confirmed by P-31 NMR spectroscopy. Hot stage optical polarized microscope (HOPM) analysis revealed that all the polymers have a liquid- crystalline property. The char yields of the synthesized similar polymers were much higher than those of nonphosphorus polymers already reported in the literature. DSC analysis confirmed our predictions over the liquid-crystalline property, glass-transition temperature, isotropization temperature, and thermal stability of the polymers. The effects of substitution on the side chain, structure of the liquid-crystalline phase, and thermal stability of the polymers have also been discussed.